Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
  • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/0041—Photosensitive materials providing an etching agent upon exposure
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/075—Silicon-containing compounds
  • G03F7/0752—Silicon-containing compounds in non photosensitive layers or as additives, e.g. for dry lithography
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
  • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
  • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
  • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
  • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
  • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
  • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
  • H01L21/308—Chemical or electrical treatment, e.g. electrolytic etching using masks
  • H01L21/3081—Chemical or electrical treatment, e.g. electrolytic etching using masks characterised by their composition, e.g. multilayer masks, materials
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
  • Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
  • Y10S430/1055—Radiation sensitive composition or product or process of making
  • Y10S430/106—Binder containing
  • Y10S430/108—Polyolefin or halogen containing
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
  • Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
  • Y10S430/1055—Radiation sensitive composition or product or process of making
  • Y10S430/114—Initiator containing
  • Y10S430/115—Cationic or anionic

Definitions

• the present invention is concerned with new photoresists for use in the manufacture of microelectronic devices such as those used in microelectromechanical systems (MEMS).
• MEMS microelectromechanical systems
• etch protective coatings or masks for MEMS fabrication processes have been selected primarily by using a trial-and-error method because there are no general purpose protective coatings on the market.
• the etch selectivity of the etchants to various materials is often used as a guide for MEMS process engineers.
• films of silicon nitride have been used as a protective layer or hardmask during KOH or TMAH bulk silicon etching.
• Silicon dioxide has a higher etch rate than silicon nitride. Therefore, it is only used as a protective/mask layer for very short etches.
• Gold (Au), chromium (Cr), and boron (B) have also been reportedly used in some situations.
• Non-patterned, hard-baked photoresists have been used as masks, but they are readily etched in alkaline solutions.
• Polymethyl methacrylate was also evaluated as an etch mask for KOH. However, because of saponification of the ester group, the masking time of this polymer was found to decrease sharply from 165 minutes at 60 0 C to 15 minutes at 90 0 C.
• a photoresist layer to be patterned must be applied to the protective coating or mask so that the pattern can be transferred to the underlying substrate.
• this can only be carried out after the protective coating or mask has been applied, thus requiring time and expense to apply and later etch this protective layer or mask, which is very difficult to remove.
• the present invention overcomes these problems by providing spin-applied, photosensitive coating systems that replace prior art masks or protective coatings, and that eliminate the need for additional photoresists in the system.
• the inventive systems protect device featuies from corrosion and other forms of attack during deep-etching processes that utilize concentrated aqueous bases.
• the invention provides a photosensitive composition useful as a protective layer.
• the composition comprises a polymer and a photoacid generator, and the polymer comprises styrene-containing monomers, acrylonitrile-containing monomers, and epoxy-containing monomers.
• the invention also provides methods of using these photosensitive compositions in conjunction with a primer layer to form microelectronic structures.
• these systems comprise a primer layer that is applied to a microelectronic substrate surface, and a photosensitive layer that is applied to the primer layer.
• Preferred primer layers are formed from primer layer compositions including a silane dispersed or dissolved in a solvent system.
• Aromatic and organo silanes are particularly preferred silanes for use in the primer layers of the invention.
• the silane include at least one (and more preferably 2-3) group per mole of compound, or per repeat unit of polymer, that reacts with epoxy groups to form
• _?_ covalent bonds so that adhesion to a silicon substrate is very strong.
• One preferred such group is an amine group.
• Preferred silanes include aminoalkoxysilanes, preferably from about C 1 to about
• the aminoalkoxysilane is an aminoalkylalkoxysilane, preferably from about C 1 to about C 8 alkyls, more preferably from about C 1 to about C 4 alkyls, and even more preferably from about C 1 to about C 3 alkyls. Phenylaminoalkylalkoxysilanes are also preferred.
• Some examples of the foregoing include aminopropyltrimethoxysilane, aminopropyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, N- phenylaminopropyltriethoxysilane, 3 -glycidoxypropyltrimethoxysilane, 2-(3 ,4- epoxycyclohexyl)ethyltrimethoxysilane, and 3-mercaptopropyl-trimethoxysilane.
• silanes include phenylsilanes such as phenyltrimethoxysilane, phenyltrichlorosilane, phenyltriethoxysilane, phenyltriacetoxysilane, and diphenylsilanes such as diphenyldimethoxysilane, diphenyldichlorosilane, and diphenylsilanediol.
• phenylsilanes such as phenyltrimethoxysilane, phenyltrichlorosilane, phenyltriethoxysilane, phenyltriacetoxysilane
• diphenylsilanes such as diphenyldimethoxysilane, diphenyldichlorosilane, and diphenylsilanediol.
• silanes include 2-phenylethyltrialkoxysilane, p/m-chlorophenyltrimethoxysilane, p/m-bromophenyltrimethoxysilane,(p/m- chloromethyl)phenyltrimethoxysilane, 2-(p/m-methoxy)phenylethyltrimethoxysilane,
• each of i, j, and k is individually selected from the group consisting of 0 and 1, and if one of i and j is I 5 then the other of i and j is 0; each R 4 is individually selected from the group consisting of hydrogen, the halogens, C 1 -C 8 (preferably C 1 -C 4 ) alkyls, C 1 -C 8 (preferably C 1 -C 4 ) alkoxys, C 1 -C 8 (preferably C 1 -C 4 ) haloalkyls, aminos, and C J -C 8
• each R 5 is individually selected from the group consisting of C 1 -C 8 (preferably
• each R 6 is individually selected from the group consisting of hydrogen and haloalkyls (preferably C 1 -C 8 , more preferably C 1 -C 4 ); each X is individually selected from the group consisting of halogens, hydroxyls, C 1 -C 4 alkoxys and C 1 -C 4 carboxyls;
• An effective primer layer composition according to the invention is a mixture of a diphenyldialkoxysilane (e.g., diphenyldimethoxysilane) and a phenyltrialkoxysilane, (e.g., phenyltrimethoxysilane) or, even more preferably, a mixture of diphenylsilanediol and phenyltrimethoxysilane in a solution of 1 -methoxy-2- propanol or l-propoxy-2-propanol with from about 5-10% by weight water.
• a diphenyldialkoxysilane e.g., diphenyldimethoxysilane
• a phenyltrialkoxysilane e.g., phenyltrimethoxysilane
• a particularly effective primer layer composition for photosensitive layers comprising a poly(styrene-co-acrylonitrile) polymer is an alcohol and water solution containing from about 0.1-1.0% (preferably from about 0.25-0.5%) by weight diphenylsilanediol and from about 0.1-1.0% (preferably from about 0.25-0.5%) by weight of phenyltrimethoxysilane.
• diphenylsilanediol and phenylsilanetriol the hydrolysis product of phenyltrimethoxysilane
• Another preferred silane has the formula
• each R 7 is individually selected from the group consisting of hydrogen, the halogens, C 1 -C 8 (preferably C 1 -C 4 ) alkyls, C 1 -C 8 (preferably C r C 4 ) alkoxys, C 1 -C 8 (preferably C 1 -C 4 ) haloalkyls, aminos, and C 1 -C 8 (preferably C 1 -C 4 ) alkylaminos; and each R 8 is individually selected from the group consisting of C 1 -C 8 (preferably C 1 -C 4 ) alkyls; and each R 8 is individually selected from the group consisting of C 1 -C 8 (preferably C 1 -C 4 ) alkyls; and each R 8 is individually selected from the group consisting of C 1 -C 8 (preferably C 1 -C 8 (preferably C 1 -C 4 ) alkylaminos; and each R 8 is individually selected from the group consisting of C 1 -C 8 (preferably C 1 -C 8 (preferably C 1
• Silanes having this structure are not only compatible with styrene-containing copolymers, but they are also reactive with ester, benzyl chloride, and/or epoxy groups, and they are excellent adhesion promoters.
• One particularly preferred silane within the scope of this formula is
• This silane is 3-[N-phenylamino]propyltrimethoxysilane (mentioned above), and it is commercially available from Lancaster Synthesis and Gelest Corporation.
• the silane should be included in the primer layer composition at a level of from about 0.1% to about 3% by weight, preferably from about 0.2% to about 2% by weight, and even more preferably from about 0.5% to about 1 % by weight, based upon the total weight of solids in the primer layer composition taken as 100% by weight
• the solvent system utilized in the primer layer composition should have a boiling point of from about 100 0 C to about 220 0 C, and preferably from about 140° C to about 180 0 C.
• the solvent system should be utilized at a level of from about 30% to about 99.9% by weight, and preferably from about 40% to about 80% by weight, based upon the total weight of the primer layer composition taken as 100% by weight.
• Preferred solvent systems include a solvent selected from the group consisting of methanol, ethanol, isopropanol, butanol, l-methoxy-2-propanol, ethylene glycol monomethyl ether, and l-propoxy-2-propanol, and mixtures thereof.
• water is included in the solvent system at a level of from about 20% to about 60% by weight, and preferably from about 20% to about 40% by weight, based upon the total weight of the primer layer composition taken as 100% by weight.
• the primer layer composition can also include a catalyst.
• Suitable catalysts include any inorganic or organic acid (e.g., hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid) or an inorganic or organic base (e.g., potassium hydroxide, TMAH, ammonia, amines).
• the catalyst is preferably present in the primer layer composition at levels of from about 0.01% to about 0.5% by weight, more preferably from about
• the primer layer can also include a number of optional ingredients, such as a surfactant.
• a surfactant such as FC4430 (available from 3M) or Triton X-100 (available from 3M) can be added to make a uniform primer coating that is defect-free.
• the photosensitive layer is formed from a composition comprising a polymer dispersed or dissolved in a solvent system.
• a preferred polymer is a terpolymer comprising recurring: styrene monomers; acrylonitrile monomers; and monomers comprising functional groups that react with amines.
• Preferred styrene monomers have the formula
• Preferred acrylonitrile monomers have the formula
• Preferred monomers comprising functional groups for reacting with amines include monomers comprising one or more epoxy groups (e.g., glycidylmethacrylate, glycidyl acrylate, vinylbenzyl glycidyl ether).
• epoxy groups e.g., glycidylmethacrylate, glycidyl acrylate, vinylbenzyl glycidyl ether.
• each R 1 is individually selected from the group consisting of hydrogen and C 1 -C 8 (and preferably C 1 -C 4 ) alkyls; and each R 2 is individually selected from the group consisting of hydrogen, C 1 -C 8 (and preferably C 1 -C 4 ) alkyls, and C 1 -C 8 (and preferably C 1 -C 4 ) alkoxys.
• the polymer preferably comprises from about 35% to about 75% by weight of monomer (T), more preferably from about 40% to about 70% by weight of monomer (I), and even more preferably from about 50% to about 65% by weight of monomer (I).
• the polymer preferably comprises from about 20% to about 40% by weight of monomer (JI), more preferably from about 25% to about 35% by weight of monomer (IT), and even more preferably from about 25% to about 30% by weight of monomer (II) .
• the polymer preferably comprises from about 5 % to about 15 % by weight of monomer (III), more preferably from about 6% to about 12% by weight of monomer (III), and even more preferably from about 8% to about 10% by weight of monomer (El).
• Each of the above percentages by weight is based upon the total weight of the polymer taken as 100% by weight.
• the polymer have a weight average molecular weight of from about 10,000 Daltons to about 80,000 Daltons, preferably from about 20,000 Daltons to about 60,000 Daltons, and even more preferably from about 30,000 Daltons to about
• Monomers other than monomers (I) 5 (D), and (HT) can also be present in the polymer, if desired.
• the combined weight of monomers (I), (II), and (III) in the polymer is preferably at least about 60% by weight, and more preferably from about 70% to about 90% by weight, based upon the total weight ofthe polymer taken as 100%byweight.
• suitable other monomers include those having functional groups that can react with groups in the primer layer for achieving chemical bonding between the two layers.
• These monomers may have, by way of example, haloalkyl (e.g., benzyl chloride, 2-chloroethyl methacrylate), ester (methacrylates, acrylates, maleates, fumarates, isocyanates), or anhydride functional groups, which react readily with functional groups such as hydroxyl, amino, or oxiranyl groups that can be present in the primer layer.
• haloalkyl e.g., benzyl chloride, 2-chloroethyl methacrylate
• ester methacrylates, acrylates, maleates, fumarates, isocyanates
• anhydride functional groups which react readily with functional groups such as hydroxyl, amino, or oxiranyl groups that can be present in the primer layer.
• the polymer should be included in the photosensitive layer composition at a level of from about 90% to about 98% by weight, and preferably from about 90% to about 95% by weight, based upon the total weight of solids in the photosensitive layer composition taken as 100% by weight.
• the photosensitive composition will also comprise a photoacid generator
• PAG The PAG generates a strong acid or superacid when exposed to actinic radiation such as UV light.
• suitable PAGs include those selected from the group consisting of triarylsulfonium hexafluoroanthnonate, triarylsulfonium hexafluoro- phosphate, diaryliodonium hexafluoroantimonate, diaryliodonium hexafluorophosphate,
• each R 3 is individually selected from the group consisting OfC 3 H 7 , C 8 H 17 , CH 3 C 6 H 4 , and camphor.
• the PAGs of formulas (TV) and (V) are sold by Ciba Specialty Chemicals as The CGI 13XX Family and The CGI 26X Family, respectively.
• the PAG should be included in the photosensitive composition at a level of from about 2% to about 10% by weight, and preferably from about 5% to about 8% by weight, based upon the total weight of solids in the photosensitive composition taken as 100% by weight.
• the solvent system utilized in the photosensitive composition should have a boiling point of from about 120 0 C to about 200 0 C, and preferably from about 130 0 C to about 180 0 C.
• the solvent system should be utilized at a level of from about 70% to about 95% by weight, and preferably from about 80% to about 90% by weight, based upon the total weight of the photosensitive composition taken as 100% by weight.
• Preferred solvent systems include a solvent selected from the group consisting of methyl isoamyl ketone, di(ethylene glycol) dimethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, cyclohexanone, and mixtures thereof.
• Preferred substrates for use in this process include those comprising silicon.
• Some particularly preferred substrates are selected from the group consisting of Si substrates, SiO 2 substrates, Si 3 N 4 substrates, SiO 2 on silicon substrates, Si 3 N 4 on silicon substrates, glass substrates, quartz substrates, ceramic substrates, semiconductor substrates, and metal substrates.
• the silane and any other components are dissolved in the primer solvent system to form the silane composition.
• This composition is then spin-applied onto the substrate at about 500-5,000 rpm, and preferably from about 1000-3,000 rpm, for about 30-90 seconds, and preferably for about 60 seconds. It is then baked at a temperature of from about 60-110 0 C for about 60-180 seconds (preferably about 120 seconds), and then at about 150-250 0 C for about 60-180 seconds (preferably about 120 seconds) in order to condense the silane molecules into a continuous film that is bonded to surface hydroxyl groups present on typical microelectronic substrates. That is, the hydrolyzed silane reacts with the silanol groups present in the silicon-containing substrate and also self- crosslinks by condensation. It is preferred that the primer layer have an average thickness (as measured by an ellipsometer over 5 different points) of less than about 50 nm and more preferably from about 20 nm to about 30 nm.
• the polymer, PAG, and any other components are dissolved in the solvent system and spin coated onto the substrate at about
• the epoxy or other reactive group in the photosensitive layer polymer form covalent bonds with an amine or other reactive group on the silane of the primer layer.
• the photosensitive layer is then imaged by exposing it to UV light with a wavelength of from about 150-500 mm (e.g., about 248 ⁇ m or about 365 nm), preferably in a dose of about 500 mJ/cm 2 .
• the coating is then preferably post-exposure baked at about 110°C to about 130°C for about 2 minutes, and developed with a solvent for about 1 minute. Finally, the coating is baked at about 200 0 C to about 250 0 C for about 5 minutes.
• Exposure to light causes the PAG to generate an acid, and this acid initiates crosslinking of the polymer (preferably via the epoxy groups) in the photosensitive layer.
• the crosslinked epoxy groups will have the structure
• the exposed areas become substantially insoluble (e.g., less than about 1% by weight soluble, preferably less than about 0.05% soluble, and more preferably about 0% soluble) in typical solvent developers such as propylene glycol monomethyl ether acetate, methyl isoamyl ketone, and ethyl acetoacetate.
• solvent developers such as propylene glycol monomethyl ether acetate, methyl isoamyl ketone, and ethyl acetoacetate.
• the unexposed areas remain soluble in these developers and are thus readily removed during developing.
• the pattern can be easily transferred with no additional etching steps to remove the protective layer being needed.
• the layer systems will exhibit less than about 100 ⁇ m, preferably less than about 70 ⁇ m, and more preferably less than about 50 ⁇ m of undercutting when subjected for about 2 hours (or even about 3 hours) to etching in an approximately 30-35% by weight aqueous KOH solution having a temperature of about 83-87°C. Undercutting is determined by measuring the width of overhanging protective layer at the edge of etched areas as observed under a confocal microscope. Furthermore, the inventive protective systems will experience very little or no etchant penetration during etching processes.
• the inventive protective systems when subjected for about 2 hours (or even about 3 hours) to etching in an approximately 30-35% by weight aqueous KOH solution having a temperature of about 83-87°C, the inventive protective systems will have less than about 0.1 pinholes per cm 2 of substrate, and preferably less than about 0.05 pinholes per cm 2 of substrate, when observed under a microscope at 1OX magnification. This is different from prior art photosensitive layers, which would dissolve relatively quickly in KOH and thus required the presence of a separate protective layer such as a silicon nitride layer.
• UVI-6976 a triarylsulfonium hexafluoroantimonate; a photoacid generator obtained from Dow Chemical
• UVI-6976 a triarylsulfonium hexafluoroantimonate; a photoacid generator obtained from Dow Chemical
• N-phenylaminoproyltrimethoxysilane obtained from Gelest
• propylene glycol propyl ether obtained from General Chemical
• the primer solution in Part 3 of this Example was spin coated onto a silicon wafer at 1 ,500 rpm for 1 minute.
• the primer coating was baked at 75 0 C for 2 minutes and then at 180 0 C for 2 minutes.
• the topcoat solution of Part 2 of this Example was then spin coated over the primer layer at 1,500 rpm for 1 minute.
• the topcoat was baked at 100 0 C for 2 minutes.
• the coating was imaged by exposing it to UV light at a wavelength of 365 nm in a dose of 500 mJ/cm 2 , baking at 130 0 C for 2 minutes, and developing with acetone for 1 minute. Finally, the combination was baked at 230 0 C for 5 minutes. A negative pattern was obtained.
• a solution was made by dissolving 27.07 g of styrene, 10.00 g of acrylonitrile, 3.08 g of glycidyl methacrylate, and 0.51 g of dicumyl peroxide (obtained from Aldrich) in 160 g of PGMEA.
• the solution was heated to 120 0 C under nitrogen while undergoing magnetic stirring.
• the polymerization was allowed to proceed at 120 ° C for 24 hours.
• the actual yield was determined by solids analysis to be 95.5% of the theoretical yield.
• the primer solution of Part 2 of Example 1 was spin coated onto a silicon wafer at 1,500 rpm for 1 minute.
• the primer coating was baked at 60 0 C for 5 minutes and at 180 0 C for 2 minutes.
• the topcoat solution from Part 2 of this Example was then spin coated onto the wafer at 1,500 rpm for 1 minute.
• the topcoat was baked at 100 0 C for 2 minutes.
• After the coating was imaged by exposing it to UV light at 254 nm in a dose of 500 mJ/cm 2 , it was baked at 130 ° C for 2 minutes and then developed with PGMEA for 1 minute.
• the coating was finally baked at 230 ° C for 5 minutes. A negative pattern was obtained.
• a solution was made by dissolving 168.0 g of styrene, 84.0 g of acrylonitrile, 28.3 g of glycidyl methacrylate, and 7.0 g of dicumyl peroxide in 1,120 g of PGMEA. The solution was heated to 120 0 C under nitrogen while undergoing magnetic stirring.
• the polymerization was allowed to proceed at 120 0 C for 28 hours. The actual yield was found by solid analysis to be 97.5% of the theoretical.
• the terpolymer was precipitated in isopropanol, filtered, and dried overnight under vacuum at 50 0 C.
• N-phenylaminopropyltrimethoxysilane were dissolved in a mixture of 77.50 g of propylene glycol propyl ether (PnP), 120.14 g of deionized water, 0.51 g of acetic acid, and 0.03 g of FC4430 (a surfactant).
• PnP propylene glycol propyl ether
• FC4430 a surfactant
• the primer solution prepared in Part 3 of this Example was spin coated onto a silicon wafer at 1,500 rpm for 1 minute.
• the primer coating was baked at 110 0 C for
• Example was spin coated over the primer layer at 1,500 rpm for 1 minute.
• the topcoat was baked at 110 0 C for 2 minutes.
• the coating was imaged by exposing it to UV light at a wavelength of 365 nm in a dose of 500 mJ/cm 2 , baking at 130 0 C for 2 minutes, and developing with PGMEA for 1 minute. Finally, the combination was baked at 230 0 C for 5 minutes. A negative pattern was obtained. 5.
• the wafer prepared and patterned in Part 4 of this Example was etched in 30% KOH aqueous solution at 75 0 C for 4 hours.
• the silicon was etched 178 ⁇ m deep in the areas without the polymer coating.
• the polymer-coated area remained intact.
• the pattern was transferred to the silicon wafer in essentially the same manner as prior art silicon nitride masking methods.

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